WO2020148186A1 - Zéolites cha d'aluminosilicate à petits pores chargées en fer et procédé de fabrication de zéolites cha d'aluminosilicate à petits pores chargées en métal - Google Patents

Zéolites cha d'aluminosilicate à petits pores chargées en fer et procédé de fabrication de zéolites cha d'aluminosilicate à petits pores chargées en métal Download PDF

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Publication number
WO2020148186A1
WO2020148186A1 PCT/EP2020/050539 EP2020050539W WO2020148186A1 WO 2020148186 A1 WO2020148186 A1 WO 2020148186A1 EP 2020050539 W EP2020050539 W EP 2020050539W WO 2020148186 A1 WO2020148186 A1 WO 2020148186A1
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WIPO (PCT)
Prior art keywords
iron
aluminosilicate zeolite
loaded
metal
zeolite
Prior art date
Application number
PCT/EP2020/050539
Other languages
English (en)
Inventor
Juergen Bauer
John Leonello Casci
Ralf Dotzel
Joerg Muench
Ralitsa PUROVA
Wilhelm Schwieger
Ameen SHAHID
Selvam Thangaraj
Tobias WEISSENBERGER
Original Assignee
Friedrich-Alexander-Universität Erlangen-Nürnberg
Johnson Matthey Catalysts (Germany) Gmbh
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Filing date
Publication date
Application filed by Friedrich-Alexander-Universität Erlangen-Nürnberg, Johnson Matthey Catalysts (Germany) Gmbh filed Critical Friedrich-Alexander-Universität Erlangen-Nürnberg
Priority to EP20700575.2A priority Critical patent/EP3911602A1/fr
Priority to CN202080007424.4A priority patent/CN113811511A/zh
Priority to BR112021012478-0A priority patent/BR112021012478A2/pt
Priority to JP2021539614A priority patent/JP2022516755A/ja
Priority to KR1020217020572A priority patent/KR20210114942A/ko
Publication of WO2020148186A1 publication Critical patent/WO2020148186A1/fr

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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
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    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
    • C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
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    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • F01N3/2066—Selective catalytic reduction [SCR]
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2839—Arrangements for mounting catalyst support in housing, e.g. with means for compensating thermal expansion or vibration
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Definitions

  • the present invention relates to an iron-loaded aluminosilicate zeolite having a maximum pore opening defined by eight tetrahedral atoms - defined herein as being“small pore” - and having the framework type CHA, AEI, AFX, ERI or LTA, and wherein the iron (Fe) is present in a range of from about 0.5 to about 5.0 wt.% based on the total weight of the iron-loaded aluminosilicate zeolite.
  • the invention also relates to a method of making metal- loaded small pore aluminosilicate zeolites.
  • Certain metal loaded zeolites for example, iron-(Fe)loaded zeolites, demonstrate relatively high catalytic activity in several reactions such as direct N2O decomposition, direct oxidation of benzene to phenol and selective catalytic reduction of nitric oxide and/or nitrogen dioxide by ammonia (NH 3 -SCR) and have been extensively investigated.
  • NH 3 -SCR ammonia
  • the selective catalytic reduction of nitrogen oxides (NO x ) by ammonia (NH 3 -SCR) is considered to be the most practical and efficient technology for the abatement of NO x from exhaust gases emitted from the stationary sources and mobile engines, principally diesel engines, for vehicles such as automobiles, trucks, locomotives and ships.
  • the nature and distribution of iron species in Fe-loaded zeolites largely depend on the catalyst preparation method, which thus determines the Fe-loaded zeolite’s resulting catalytic activity.
  • Several methods have been mentioned in the literature for preparing Fe-loaded zeolites, including wet impregnation, wet ion exchange, solid state ion exchange, chemical vapour deposition and direct synthesis procedures.
  • a problem associated with the preparation of Fe-loaded synthetic zeolites by post-synthesis treatment is the aggregation of iron species, which leads to a heterogeneous distribution of iron species in the zeolite ZSM-5 (MFI) (see e.g. L. Kustov et al, Topics in Catalysis, 238 (2006) pp. 250-259).
  • MFI zeolite ZSM-5
  • IUPAC IUPAC
  • micropores pore diameter dP up to 2 nm
  • mesopores dP from 2 to 50 nm
  • macropores dP greater than 50 nm
  • Hierarchical zeolites can have either micropores and mesopores, micropores and macropores or all three porosity levels [Chen et al. J. Mater. Chem., 22 (2012) 17381], with the decisive criterion for hierarchy being the crosslinking between the various porosity levels. It is known to synthesise micro-mesoporous hierarchically structured zeolitic materials, which integrate at least two levels of porosity, using e.g. organic molecules such as polymers and surfactants as mesopore templates in addition to regular micropore templates. Macropores can be introduced into zeolites through sphere templating, post-synthetic modifications, and templating with macroporous supports. A technique of making microporous-macroporous zeolite MFI is disclosed in A.G. Machoke et al, Adv. Mater. 2015, 27, 1066-1070.
  • Zeolites can also be categorised by pore size, e.g. a maximum number of tetrahedral atoms present in a zeolite’s framework.
  • a“small pore” zeolite such as CHA
  • a“medium pore” zeolite e.g. MFI
  • a“large pore” zeolite such as BEA
  • BEA contains a maximum ring size of twelve tetrahedral atoms.
  • a small pore zeolite still has a maximum ring size of eight tetrahedral atoms. It is known that relatively good low temperature (200-450°C) NH3-SCR catalytic activity can be obtained from Cu-SSZ-13 (CHA) zeolites (see e.g. International patent publication no. WO2008/132452 A2).
  • CHA Cu-SSZ-13
  • Fe-loaded zeolites exhibit relatively higher temperature catalytic activity than Cu-containing zeolites and so Fe-loaded zeolites are of particular interest for NH3-SCR applications.
  • Cu-containing zeolites can lead to formation of N2O at higher reaction temperatures.
  • WO 2008/132452 A2 disclosed a process of preparing a 3wt% Fe-SSZ-13 sample from a commercially available sample of SSZ-13 by firstly ion-exchanging in a solution of NH4NO3 to produce a NH4 + SSZ-13, which was filtered and then added to an aqueous solution of Fe(N0 3 ) 3 with stirring. The slurry was filtered, then washed and dried and the final product was calcined to produce a so-called“fresh” product.
  • the fresh 3wt% Fe-SSZ-13 was severely lean hydrothermally aged at 900°C for 1 hour in 4.5% H O/air mixture and the resulting aged product was tested for NH3-SCR activity according to Example 6.
  • the results for NO x conversion at 350°C and 450°C are discussed at Example 14 and shown in Figure 19.
  • the fresh, i.e. un-aged, 3wt% Fe-SSZ-13 was also tested for NH3-SCR activity at 300°C and 350°C according to Example 22 in a synthetic gas composition wherein a NO x component consisted of NO only or a 1 : 1 mixture of both NO and NO2. The results are shown in Figure 20.
  • WO 2008/118434 A1 discloses at Example 3 and Table 1 a so-called high-silica chabazite (CHA) synthesised according to examples in US patent no. 4544538 and having a silica-to-alumina ratio of 28.
  • Table 1 discloses that the CHA material of Example 3 was Fe ion-exchanged with 1.4wt% Fe 2 0 3 but there is no explanation of the methodology used.
  • US patent publication 2018/0237307 discloses a chabazite-type zeolite and a method of making it, to which iron may be introduced by post-synthesis addition. However, none of the Examples explains how the iron was added.
  • the small pores of the CHA zeolite tend to impede ion-exchange of the iron species into the zeolite framework resulting in partial exchange of the iron ions to the Bronsted sites and potentially the formation of larger iron oxide particles.
  • R.Q. Long et ak J. Cat. 207, 274-285 (2002) discloses the preparation of Fe-(natural)CHA for selective catalytic reduction of NO with ammonia.
  • the natural CHA used had a Si/Al ratio of 2, i.e. a silica-to-alumina ratio of 4.
  • the natural CHA was first transformed to MFt-zeolite by exchanging with 0.5M NH4CI solution (4 times) at room temperature.
  • a conventional ion-exchange procedure was used to prepare the ion-exchanged product wherein 2 g of the NTLt-zeolite was added to 200ml of 0.05M FeCh solution with constant stirring for 24 hours followed by washing five times with deionized water.
  • the obtained catalyst was first dried at 120°C in air for 12 hours, then calcined at 500°C for 6 hours.
  • the resulting catalyst was said to have an ion-exchange level of 56%.
  • the catalytic activity measured in a fixed-bed quartz reactor using a synthetic flue gas of lOOOppm NO, lOOOppm N3 ⁇ 4, 2% O2 and balance He was relatively poor compared with Fe-(synthetic) mordenite (MOR), Fe-beta (BEA), Fe-ferrierite (FER) and Fe-(natural) clinoptilolite (HEU).
  • the zeolites can be zeolite beta (BEA), ZSM-5 (MFI), faujasite, ferrierite, Y, ZSM-20, MCM-41, chabazite or SAPO, but preferably MFI, which is exemplified, or zeolite beta.
  • the resulting catalysts are pale yellow to beige in colour, which is said to be indicative of an iron oxidation state below Fe 3+ , i.e. Fe 2+ , whereas a rust-red colour would indicate Fe 3+ .
  • the Integral UV-Vis signal (a.u.) for the FeiC particles shown in Figure 3) show that iron oxide (FeiC ) particles are present in the catalysts at Fe loadings above about 0.4 wt.%. So, despite the claims made in the publication, the facts presented by the authors themselves would appear to indicate that the procedure does not avoid a heterogeneous distribution of iron species as the iron loading increases from a relatively low loading and a ratio of an integral UV-Vis signal (arbitrary units (a.u.)) of the iron monomer at about 270nm to oligomer at about 350nm at about 1.0 wt.% Fe is ⁇ 2.
  • the invention provides an iron-loaded aluminosilicate zeolite having a maximum pore opening defined by eight tetrahedral atoms and having the framework type CHA, AEI, AFX, ERI or LTA, wherein the iron (Fe) is present in a range of from about 0.5 to about 5.0 wt.% based on the total weight of the iron-loaded aluminosilicate zeolite, wherein an ultraviolet-visible absorbance spectrum of the iron-loaded aluminosilicate zeolite comprises a band at approximately 280nm, wherein a ratio of an integral, peak-fitted ultraviolet-visible absorbance signal measured in arbitrary units (a.u.) for the band at approximately 280nm to an integral, peak-fitted ultraviolet-visible absorbance signal measured in arbitrary units (a.u.) for a band at approximately 340nm is > about 2.
  • the selected framework types are CHA, AEI and AFX, most preferably
  • the art has attributed an integral, peak-fitted ultraviolet-visible absorbance spectrum band to the following iron species for zeolites of the claimed framework types: (i) at approximately 280nm for the iron-loaded synthetic aluminosilicate zeolites of the claimed framework types to isolated octahedrally co-ordinated Fe 3+ sites; (ii) at approximately 340nm to oligomeric Fe 3+ sites; and (iii) at approximately 470nm to iron oxide (FeiCb) particles. See also the under the“Physicochemical Characterisation” section in Example 2 hereinbelow.
  • iron species according to the first aspect of the invention are predominantly present as isolated iron species.
  • “Predominantly” as used herein has its ordinary English meaning of“>50%”.
  • the definition“isolated iron species” herein shall mean“not present as Fe2C>3 particles”.
  • the basic and novel characteristics of the first aspect of the present invention are an iron-loaded synthetic aluminosilicate zeolite comprising a ratio of an integral, peak-fitted ultraviolet-visible absorbance signal measured in arbitrary units (a.u.) for a band at approximately 280nm attributable to isolated octahedrally-coordinated Fe 3+ sites to a band at approximately 340nm attributable to oligomeric Fe 3+ sites is > about 2 and a method of making such iron-loaded synthetic aluminosilicate zeolite.
  • the term“consisting of’ closes the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith.
  • US patent publication no. 2017/0267537 A1 discloses a method of producing zeolitic monocrystals, each of which having a pore system comprising at least one micropore system and at least one macropore system, wherein porous oxide particles are converted into the zeolitic material in the presence of an organic template and steam.
  • US 2008/193358 A1 discloses a method of producing a catalytically active mineral based on a tectosilicate for reducing NO x to N2 using either hydrocarbon fuel or ammonia, optionally derived from urea, as reducing agent.
  • the tectosilicate is preferably a natural zeolite, which is first treated to replace naturally occurring alkali metal and alkaline earth metal counter ions with a metal salt solution before exchanging the treated natural zeolite in the H + form with a transition metal salt, preferably a copper and/or an iron salt.
  • Chabazite is mentioned as a possible natural zeolite but is preferably a heulandite and most preferably a clinoptilolite.
  • the metal salt solution used to replace the naturally occurring counter ions is preferably an ammonium nitrate chloride/ammonium nitrate solution.
  • an ammonium nitrate chloride/ammonium nitrate solution As natural zeolites have a relatively low silica-to-alumina ratio, even if the ammonium nitrate chloride/ammonium nitrate solution were particularly alkaline, it would not be expected to lead to desilication and the introduction of mesoporosity.
  • the terms“micropore” and“mesopore” use the IUPAC convention mentioned hereinabove.
  • the pore diameters can for example be determined by means of imaging techniques, e.g. electron micrographs, or by means of electron beam tomography. The latter is also suitable for determining pore diameters on the inside of crystals.
  • sorption processes using gases (in particular for the diameters of micro or mesopores) or penetration methods using mercury (in particular for the diameters of the macropores) can be used.
  • the iron-loaded aluminosilicate zeolites according to the first aspect can be further distinguished by a ratio of integral ultraviolet-visible absorbance signal measured in arbitrary units (a.u.) for the band at approximately 280nm to an integral ultraviolet-visible absorbance signal measured in arbitrary units (a.u.) for a band at approximately 470nm is > about 5.
  • the iron-loaded aluminosilicate zeolites according to the first aspect may preferably have the framework type CHA, AEI or AFX, most preferably CHA (synthetic or natural) or AEI (synthetic only).
  • the aluminosilicate zeolite is preferably a synthetic aluminosilicate zeolite.
  • the aluminosilicate zeolite is synthetic CHA.
  • the natural zeolites of the framework types according to the invention are CHA or ERI, preferably CHA.
  • the iron present in iron-loaded aluminosilicate zeolite according to the invention can be in the range of from about 0.27 to about 3.0 wt.% based on the total weight of the iron- loaded aluminosilicate zeolite, such as from about 0.7 to about 3.0 wt.% or about 0.27 to about 1.20 wt.% or about 1.20 to about 3.00 wt.%.
  • the iron-loaded synthetic aluminosilicate zeolite according to the first aspect of the invention preferably has a silicon-to-aluminium ratio of the underlying aluminosilicate zeolite of from about 5 to about 15 corresponding to a silica-to-alumina ratio of about 10 to about 30.
  • the Fe/Al atomic ratio of an iron-loaded synthetic aluminosilicate zeolite according to the invention can be from about 0.032 to about 0.75, corresponding to a silicon-to-aluminium ratio of about 5 to about 15 and an iron content of about 0.5 to about 5.0 wt.% based on the total weight of the iron-loaded aluminosilicate zeolite.
  • the Fe/Al atomic ratio of an iron- containing natural aluminosilicate zeolite according to the invention can be from about 0.015 to about 0.28, corresponding to a silicon-to-aluminium ratio of about 2 to about 5 and an iron content of about 0.5 to about 5.0 wt.% based on the total weight of the iron-loaded aluminosilicate zeolite.
  • the iron-loaded synthetic aluminosilicate zeolite according to the invention has a mesopore volume determined by nitrogen physisorption of > about 0.10 cm 3 /g; optionally a total pore volume of > about 0.30 cm 3 /g.
  • the iron-loaded synthetic aluminosilicate zeolite according to invention comprises one or more than one of the transition elements selected from the group consisting of Ce, Cu, Mn, Pd and Pt.
  • cerium is considered to be atransition metal, i.e. a lanthanoid inner transition element belonging to period 6
  • the invention provides a honeycomb monolith substrate comprising an iron-loaded aluminosilicate zeolite according to the first aspect of the invention, wherein the honeycomb monolith substrate is coated with a washcoat composition according to the second aspect of the invention or the honeycomb monolith substrate comprises an extrusion of the iron-loaded aluminosilicate zeolite.
  • the invention provides an exhaust system comprising an injector for injecting a nitrogenous reductant from a source of nitrogenous reductant into a flowing exhaust gas and a source of nitrogenous reductant, which injector is disposed upstream from a honeycomb monolith substrate according to the third aspect of the invention.
  • the exhaust system comprises a honeycomb monolith substrate comprising an oxidation catalyst for oxidising nitrogen monoxide in an exhaust gas flowing in the system to nitrogen dioxide, which honeycomb monolith substrate comprising the oxidation catalyst is disposed upstream of the honeycomb monolith substrate comprising the iron-loaded synthetic aluminosilicate zeolite.
  • the invention provides the use of an iron-loaded aluminosilicate zeolite according to the first aspect of the invention for selectively reducing oxides of nitrogen in an exhaust gas to dinitrogen using a nitrogenous reducing agent.
  • the invention provides a method of making a metal-loaded aluminosilicate zeolite having a maximum pore opening defined by eight tetrahedral atoms from pre-existing aluminosilicate zeolite crystallites, wherein the metal is present in a range of from 0.5 to 5.0 wt.% based on the total weight of the metal-loaded aluminosilicate zeolite, which method comprising the steps of:
  • step (ii) introducing the metal into the product of step (i) by wet impregnation or wet ion- exchange by contacting the product of step (i) with a mixture of a metal reagent and a structure directing agent for the aluminosilicate zeolite;
  • the pre-formed aluminosilicate zeolite crystallites to be treated are crystallites of a synthetic zeolite, for example a synthetic aluminosilicate zeolite having the framework type CHA, AEI, AFX, ERI or LTA.
  • the pre-formed aluminosilicate zeolite crystallites to be treated are crystallites of a natural aluminosilicate zeolite, for example a natural zeolite having the framework type CHA or ERI.
  • the metal-loaded aluminosilicate zeolite may be a transition metal-loaded aluminosilicate zeolite, especially an iron-loaded aluminosilicate zeolite, having the framework type CHA, AEI, AFX, ERI or LTA.
  • step (i) introducing mesoporosity into the synthetic aluminosilicate zeolite crystallites by application of an aqueous alkali treatment to dissolve silica in the aluminosilicate zeolite crystallites; (ii) introducing iron into the product of step (i) by wet impregnation or wet ion- exchange by contacting the product of step (i) with a mixture of an iron reagent and a structure directing agent for the aluminosilicate zeolite; and
  • step (iii) performing hydrothermal crystallisation on the product of step (ii).
  • silica and/or alumina dissolved in step (i) may be reassembled around the metal- (e.g. iron-) impregnated mesoporous synthetic aluminosilicate crystallites produced in step (ii) to form the metal-loaded (e.g. iron-loaded) synthetic aluminosilicate zeolite.
  • the metal- e.g. iron-
  • the metal-loaded (e.g. iron-loaded) synthetic aluminosilicate zeolite e.g. iron-loaded
  • the aluminosilicate zeolite crystallites used in step (i) and/or the product of (iii) has an alkali content of the zeolite of less than about 1 weight percent more preferably less than about 0.5 weight percent, which can improve catalyst durability and overall NOx conversion in use as a SCR catalyst.
  • alkali content is expressed on a wt % basis in terms of the respective oxides for sodium, calcium and potassium present as cations in the zeolite.
  • the hydrothermal crystallisation step (iii) may comprise steam-assisted crystallisation.
  • the steam-assisted crystallisation step (iii) can, for example, be carried out by introducing the product of step (ii) or (ii’) into an autoclave containing water which, upon heating, at least partially enters the vapour phase.
  • the material to be converted should not come into contact with liquid water. Additional pressurization is not necessary.
  • the mixture provided in step (ii) can also be converted under atmospheric pressure in the presence of moist air in step (iii), e.g. in a climatic chamber or an oven.
  • the step (iii) temperature is typically between 50° C. and 250° C., preferably between 80° C and 160° C and especially preferred between 90° C and 130° C.
  • the duration of the step (iii) synthesis is usually between 12 h (hours) and 10 d (days), however, preferably between 1 day and 5 days, and especially preferred between 2 days and 4 days.
  • the reaction mixture is left to cool.
  • the product can then be subjected to common aftertreatment steps such as washing.
  • one of the advantages of the method according to the present invention is the fact that the resulting product is already macroporous after synthesis so that the aftertreatment steps common after synthesis in other methods to remove the macro template can be omitted.
  • Separation techniques include centrifugation e.g. 10,000 rpm, washing e.g. 3x in distilled water.
  • a preferable structure directing agent for use in connection with the method directed to synthetic or natural aluminosilicate CHA zeolites is TMAdOH.
  • Alkali treatment is preferably used for embodiments using synthetic zeolites, which general have higher silicon-to-aluminium ratios than natural zeolites. For relatively low silicon-to-aluminium ratio natural zeolites, it is preferable to introduce mesoporosity by dissolving aluminium using acid treatment, such as oxalic acid, instead of alkali treatment.
  • acid treatment such as oxalic acid
  • step (i) uses an alkali treatment to dissolve silica, preferably the method further includes adding a surfactant to an aqueous system of step (i).
  • Typical surfactants with application according to the sixth aspect of the present invention include cationic, anionic or non-ionic surfactants.
  • Cationic surfactants that can be used include Cetyl Trimethyl Ammonium Bromide (CTAB) also known as hexadecyltrimethylyammonium bromide, a quaternary ammonium surfactant; dodecytrimethylammonium bromide (DTAB); and tetradecyltrimethylammonium bromide (TTAB).
  • CTAB Cetyl Trimethyl Ammonium Bromide
  • DTAB dodecytrimethylammonium bromide
  • TTAB tetradecyltrimethylammonium bromide
  • Anionic surfactants with application in the seventh aspect of the present invention include sodium dodecyl sulfate (SDS), sodium lauryl sulfate (SLS), sodium pareth sulfate (SPS) or sodium laureth sulfate (SLES).
  • Non-ionic surfactants include Tween 60TM.
  • Cationic surfactants may be preferable for use where alkali pH solutions are used in step (i).
  • the surfactant is a cationic surfactant and is most preferably cetyltrimethylammonium bromide (CTAB).
  • CTAB cetyltrimethylammonium bromide
  • the metal reagent can be any suitable metal reagent.
  • the metal to be loaded is iron
  • the iron-reagent may be aqueous iron nitrate.
  • an iron-loaded synthetic aluminosilicate zeolite optionally according to the first aspect of the present invention, obtained by or obtainable by the method according to the sixth aspect of the invention.
  • the properties of the material according to the present invention can optionally be optimized for specific applications by means of common post-synthetic modifications such as demetallization, ion exchange or thermal treatment known to the person skilled in the art.
  • Figure l is a schematic diagram showing the procedure for a synthetic aluminosilicate CHA embodiment according to the invention performed on SSZ-13;
  • Figure 2 shows a comparison of the powder XRD pattern of the parent SSZ-13 and post-synthesis modified materials at various steps of the procedure set out schematically in Fig. 1;
  • Figure 3 shows nitrogen physisorption analysis of the parent SSZ-13 and post-synthesis modified SSZ-13 zeolites according to the Examples;
  • Figure 5 shows UV-Vis spectra of (a) CHA22_Fel, (b) CHA22_DR_Fel, and (c) CHA22 DR F e 1 SAC ;
  • Figure 6 shows the ME -selective catalytic reduction (SCR) catalytic performance of CHA22_Fel, CHA22_DR_Fel and CHA22_DR_Fel_SAC.
  • H-form A commercially available SSZ-13 zeolite (H-form) with a nominal SiCh/AECb ratio (SAR) of 22 was used in the course of these Examples.
  • the as-received sample was labelled as H CHA22.
  • the Si/Al ratio of the H CHA22 sample measured by ICP-OES was 11.4, i.e. a silica-to-alumina ratio of 22.8.
  • the mesoporous SSZ-13 prepared as described hereinabove was first converted into its H-form. Typically, lg of sodium form zeolite powder was ion exchanged two times with 25ml of 0.2 M NH4NO3 at room temperature under stirring condition for 24 hours. The ion- exchanged powder was filtered, washed and dried at 70°C overnight. Subsequently, the post modified sample was calcined in air at 550°C for 5 hours. Wet ion exchange of sample CHA22 DR (H-form) was performed in a similar manner to that described for the microporous SSZ-13 (CHA22_Fel). The iron containing mesoporous SSZ-13 prepared by wet ion- exchange was labelled as CHA22_DR_Fel .
  • Mesoporous SSZ-13 (CHA22 DR) was mixed with an aqueous solution of iron nitrate, water, structure directing agent (TMAdOH) and sodium hydroxide so that the final composition had the composition l Si0 2 :0.05Al 2 0 3 :0.007Fe 2 0 3 :0.07Na 2 0:0.1TMAdOH:45H 2 0.
  • the mixture was stirred for 30 minutes at room temperature. Thereafter, the excess water was evaporated and dried at 60°C in an oven. The dried powder was finely ground in a mortar using a pestle and the resulting ground powder was poured into a PTFE crucible. Water was added into the liner and the crucible was mounted in the liner.
  • N 2 -physisorption at 77 Kelvin was performed in a QuadrasorbTM SI gas adsorption analyser for the surface area analysis and pore size analysis. Prior to analysis, the samples were pre-treated for 12 hours at 300°C under vacuum. For NFP-TPD, the ammonia uptake of all samples was measured using TPDRO 1100 Thermo electron cooperation. Each sample was placed between layers of quartz wool in a glass tube and then pre-treated in the helium flow at 550°C for 30 minutes with a ramp-rate of 10 °C/min. The saturation of each zeolite sample with gaseous ammonia was carried out at 120°C for 30 minutes. Finally, the ammonia was removed in the helium flow at 600°C for 60 minutes with a ramp-rate of 10°C/min. The gas exiting the glass tube was analysed using a thermal conductivity detector (TCD).
  • TCD thermal conductivity detector
  • Solid state NMR analyses were performed at 11.74 T on an Agilent DD2 500 MHz WB spectrometer equipped with a commercial 3.2 mm triple resonance MAS probe at a 29 Si and 27 A1 frequency of 99.362 MHz and 130.318 MHz, respectively.
  • 29 Si direct excitation experiments of were acquired using a 90° pulse length of 3.0 ps, recycle delay of 60 seconds and at a sample spinning frequency of 10 kHz.
  • 27 A1 magic-angle spinning (MAS) NMR spectra were obtained using direct excitation at a spin speed 15 kHz with a pulse length of 1.25 ps and a recycle delay of 1.0 seconds.
  • 29 Si and 27 A1 MAS experiments were performed with a total number of scans (NS) of 128 and 4000, respectively.
  • the Chemical Shifts of 29 Si were reported using delta scale and are referenced to tetramethyl silane (TMS) at 0 ppm.
  • Fig. 2 shows the powder XRD pattern of the parent SSZ-13 (H CHA22), iron containing samples prepared by wet ion-exchange of microporous SSZ-13 (CHA22_Fel), iron-loaded sample prepared by wet ion exchange of mesoporous SSZ-13 (CHA22_DR_Fel) and iron-loaded sample prepared by steam-assisted crystallisation of the iron-loaded mesoporous SSZ-13 (CHA22_DR_Fel_SAC).
  • the corresponding relative crystallinity of the ratio of the integral intensities of X-ray peaks in 2Q ° 13.1, 16.3, 18.1, 20.9, 25.4, 26.3,
  • Table 1 Relative crystallinity, chemical composition and acidic properties of the parent and post treated zeolites
  • ICP-OES Inductively coupled plasma-optical emission spectroscopy
  • NH 3 -TPD ammonia temperature programmed desorption
  • XRD analysis indicates that the parent sample (H CHA22) has Chabazite (CHA)-type structure without any other crystalline phase.
  • CHA Chabazite
  • the peak intensities characteristic of CHA reflections decreased, possibly due to the higher X-rays absorption coefficient of iron species.
  • the introduction of mesopores and addition of iron in mesoporous SSZ-13 (CHA22_DR_Fel) leads to interruption in the long range periodic arrangement of crystalline structure and thus results in the reduction of peak intensities.
  • the sample prepared by steam assisted crystallisation of the iron-loaded mesoporous SSZ-13 exhibits high characteristic peak intensity, which implies that the iron-loaded mesoporous SSZ-13 has been successfully recrystallized.
  • H CHA22 The nitrogen adsorption isotherm of H CHA22 follows the IUPAC Type 1 isotherm and implies that the sample has a microporous nature.
  • the pore size distribution of sample H CHA22 shows that the presence of mesopores is negligible. Addition of iron in sample H CHA22 results in less BET surface area and micropore volume.
  • the nitrogen adsorption-desorption isotherm of sample CHA22_DR_Fel_SAC has high nitrogen uptake at low P/Po and a plateau with increasing P/Po, which indicates that the mesopores which were created by desilication-reassembly are closed after the steam-assisted crystallisation.
  • the elemental analysis and the acidity measurement of the parent and post-treated samples are given in Table 1.
  • ICP analysis showed that the Si/Al ratio of the mesoporous samples prepared by the desilication-reassembly approach (CHA22 DR) is similar to the parent sample (H CHA22).
  • the sample prepared by steam-assisted crystallisation of the iron containing mesoporous SSZ-13 zeolite is also similar to the parent sample, which indicates that little or no material is lost during the steam-assisted crystallisation.
  • the iron contents of samples CHA22_Fel, CHA22_DR_Fel and CHA22_DR_Fel_SAC are 0.75, 1.1 and 0.97 wt. % respectively.
  • the SEM image analysis shows that the parent sample (H CHA22) exhibits cube like intergrown morphology of the chabazite (CHA) that appears to have a smooth surface (see Fig. 4a).
  • the amorphous silica can be observed on the external surface of the mesoporous SSZ-13 and iron-loaded mesoporous SSZ-13 zeolites (see Figs. 4b and 4c respectively).
  • the 27A1 MAS NMR spectra of mesoporous SSZ-13 zeolite (CHA22 DR) contains an intense peak at 58 ppm (tetrahedrally- coordinated aluminium), which is accompanied by a shoulder that stretches to 30 ppm and indicates the presence of pentahedrally-coordinated aluminium.
  • UV-vis spectroscopy was used to investigate the coordination state and extent of aggregation of iron species.
  • the UV-vis spectra of samples CHA22_Fel, CHA22_DR_Fel, and CHA22_DR_Fel_SAC are shown in Fig. 5.
  • the Sample CHA22_DR_Fel has clear bands at 280 and 340 nm, which are indicators of isolated octahedrally-coordinated and oligomeric Fe 3+ sites, respectively.
  • the low wavelength band from 200-220 nm is not clear, probably because this sample was prepared by wet ion exchange of mesoporous SSZ-13 (CHA22 DR), which has very low microporosity (0.05 cm 3 /g).
  • the two bands at 427 and 540 nm, for the larger iron oxide particles, are much weaker than the corresponding bands in sample CHA22_Fel, which suggests that the iron ions supported in mesoporous SSZ-13 (CHA22_DR_Fel) were less oxidised during calcination.
  • the UV-vis band of sample CHA22_DR_Fel_SAC extends from 200 to 500 nm and shows strong, defined peaks at 220 and 280 nm, which indicate isolated tetrahedrally-/ and octahedrally-coordinated Fe 3+ sites and are difficult to discriminate therebetween. Moreover, this sample has a weak band at 340 nm and so a relatively small quantity of oligomeric Fe 3+ sites. A very weak signal at 470 nm implies that sample CHA22_DR_Fel_SAC contains negligible iron oxide particles.
  • the NH 3 -SCR catalytic activity of each sample was measured in a fixed bed quartz reactor.
  • the composition of the reactant gas mixture used was 550 ppm N3 ⁇ 4, 500 ppm NO, 8 % O2, 10 % H2O with a balance of nitrogen.
  • the total gas flow rate was 840 ml/h or lOOOL/g.h WHSV (weight hourly space velocity) and a sample mass of 50mg was used.
  • CHA22_DR_Fel_SAC samples were tested and the results are presented in Fig. 6.
  • Iron-loaded mesoporous SSZ-13 (CHA22_DR_Fel) also exhibits relatively low NO conversion, although it contains a relatively high wt.% quantity of iron. This relatively low NO conversion is presumably due to the loss of crystalline structure during the desilication- reassembly process and thus can be observed in the XRD and nitrogen physisorption results (see Figs. 2 and 3 and under the“Physicochemical Characterisation” heading of Example 2).
  • Sample CHA22_DR_Fel_SAC exhibits good, relatively high NO conversion compared to the other two samples which we attribute to the presence of iron sites in SSZ-13 cages as isolated tetrahedrally-coordinated and octahedrally-coordinated and comparatively fewer oligomeric Fe 3+ sites.

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Abstract

La présente invention concerne une zéolite d'aluminosilicate chargée en fer ayant une ouverture de pore maximale définie par huit atomes tétraédriques et ayant le type de structure CHA, AEI, AFX, ERI ou LTA. Le fer (Fe) est présent dans une plage d'environ 0,5 à environ 5,0 % en poids sur la base du poids total de la zéolite d'aluminosilicate chargées en fer, un spectre d'absorbance visible dans l'ultraviolet de la zéolite d'aluminosilicate synthétique chargée en fer comprend une bande à environ 280 nm, un rapport d'un signal d'absorbance UV-visible intégré à un pic mesuré dans des unités arbitraires (au) pour la bande à environ 280 nm à un signal d'absorbance UV-visible à pic intégré mesuré dans des unités arbitraires (au) pour une bande à environ 340 nm est > à environ 2. La présente invention concerne en outre un procédé de fabrication d'une zéolite d'aluminosilicate chargée en métal ayant une ouverture de pore maximale définie par huit atomes tétraédriques à partir de cristallites de zéolite d'aluminosilicate préexistantes, le métal étant présent dans une plage de 0,5 à 5,0 % en poids sur la base du poids total de la zéolite d'aluminosilicate chargée en métal.
PCT/EP2020/050539 2019-01-14 2020-01-10 Zéolites cha d'aluminosilicate à petits pores chargées en fer et procédé de fabrication de zéolites cha d'aluminosilicate à petits pores chargées en métal WO2020148186A1 (fr)

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CN202080007424.4A CN113811511A (zh) 2019-01-14 2020-01-10 负载铁的小孔铝硅酸盐cha沸石以及制备负载金属的小孔铝硅酸盐cha沸石的方法
BR112021012478-0A BR112021012478A2 (pt) 2019-01-14 2020-01-10 Zeólito de aluminossilicato carregado com ferro, composição de revestimento, substrato monolítico em formato de colmeia, sistema de escape, uso de um zeólito de aluminossilicato carregado com ferro, e, método para fabricação de um zeólito de aluminossilicato carregado com metal
JP2021539614A JP2022516755A (ja) 2019-01-14 2020-01-10 金属担持小細孔アルミノケイ酸塩ｃｈａゼオライト及び金属担持小細孔アルミノケイ酸塩ｃｈａゼオライトの製造方法
KR1020217020572A KR20210114942A (ko) 2019-01-14 2020-01-10 철-로딩된 작은 기공 알루미노규산염 cha 제올라이트 및 금속-로딩된 작은 기공 알루미노규산염 cha 제올라이트의 제조 방법

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CN116393164A (zh) * 2023-03-30 2023-07-07 华中科技大学 助剂金属改性的Fe-SSZ-13分子筛、制备及作为脱硝催化剂的应用
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WO2023067134A1 (fr) 2021-10-22 2023-04-27 Johnson Matthey Catalysts (Germany) Gmbh Procédé et article de catalyseur

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